This invention is related to the field of polymers comprising a polymerized dialkenyl-tricyclic-nonaromatic compound and a polymerized olefin.
Polymer compounds represent a very important and highly versatile material of construction. They have become truly indispensable and are essential for clothing, shelter, transportation, and many conveniences of modern living. Therefore, there is a strong market for polymers throughout the world resulting in billions of dollars of sales per year. Most plastics can be easily fabricated into various products by such processes, for example, as blow molding, injection molding, and thermoforming. There is a significant amount of research conducted to find new polymers to supply the demand for such lightweight and versatile materials.
Processes that currently form polymers comprising a dialkenyl-tricyclic-nonaromatic compound as shown in Formula I: 
where R can be selected from the group consisting of hydrogen and alkyl groups having 1 to about 4 carbon atoms, and an olefin can produce a crosslinked polymer. Polymers that form crosslinking with each other or with other compounds can be insoluble and stable to heat. These polymers generally cannot be dissolved to allow admixture with other compounds or to flow or melt to form articles. It is desirable to produce a dialkenyl-tricyclic-nonaromratic/olefin polymer that is not crosslinked since it could be utilized for various applications.
Applicants provide such a process for producing a dialkenyl-tricyclic-nonaromatic/olefin polymer that is not crosslinked.
An object of this invention is to provide a process that produces a dialkenyl-tricyclic-nonaromatic/olefin polymer that is not crosslinked.
Another object of this invention is to provide the dialkenyl-tricyclic-nonaromatic/olefin polymer.
In accordance with one embodiment of this invention, a process to produce the dialkenyl-tricyclic-nonaromatic compound/olefin polymer is provided. The process comprises (or optionally, xe2x80x9cconsists essentially ofxe2x80x9d, or xe2x80x9cconsists ofxe2x80x9d) contacting:
1) at least one dialkenyl-tricyclic-nonaromatic compound;
2) at least one olefin;
3) at least one titanium complex; and
4) at least one aluminoxane;
in a polymerization zone under polymerization conditions to form the dialkenyl-tricyclic-nonaromatic/olefin polymer.
In accordance with another embodiment of this invention, the dialkenyl-tricyclic-nonaromatic/olefin polymer is provided.
In accordance with yet another embodiment of this invention, an article is produced comprising the dialkenyl-tricyclic-nonaromatic compound/olefin polymer.
This object, and other objects, will become more apparent to those with ordinary skill in the art after reading this disclosure.
A process to produce a dialkenyl-tricyclic-nonaromatic/olefin polymer is provided. The process comprises contacting:
1) at least one dialkenyl-tricyclic-nonaromatic compound;
2) at least one olefin;
3) at least one titanium complex; and
4) at least one aluminoxane
in a polymerization zone under polymerization conditions to form the dialkenyl-tricyclic-nonaromatic compound/olefin polymer.
The dialkenyl-tricyclic-nonaromatic compound has the formula: 
wherein R can be selected from the group consisting of hydrogen and alkyl groups having from 1 to about 4 carbon atoms. Preferably, the dialkenyl-tricyclic-nonaromatic compound is dicyclopentadiene (DCPD).
The olefin that can be used in this invention contains from 2 to about 20 carbon atoms. However, it is more preferred when the olefin contains 2 to about 10 carbon atoms. It is most preferred when the olefin has 2 to 6 carbon atoms. Olefins can be selected from the group consisting of ethylene, propylene, butylene, pentene, and hexene. Ethylene is currently most preferred.
The dialkenyl-tricyclic-nonaromatic compound and the olefin are polymerized using at least one titanium complex. The titanium complex has the following general formula:
(X1)(X2)(X3)(X4)M1
wherein M1 is titanium;
wherein (X1) is independently selected from the group consisting of cyclopentadienyls, indenyls, fluorenyls, substituted cyclopentadienyls, substituted indenyls, and substituted fluorenyls;
wherein substituents on the substituted cyclopentadienyls, substituted indenyls, and substituted fluorenyls of (X1) are selected from the group consisting of aliphatic groups, cyclic groups, combinations of aliphatic and cyclic groups, silyl groups, alkyl halide groups, halides, organometallic groups, phosphorus groups, nitrogen groups, oxygen groups such as, alkoxides and aryloxides, silicon, phosphorus, boron, germanium, and hydrogen; and
wherein (X2), (X3), and (X4) are independently selected from the group consisting of halides, aliphatic groups, substituted aliphatic groups, cyclic groups, substituted cyclic groups, combinations of aliphatic groups and cyclic groups, combinations of substituted aliphatic groups and cyclic groups, combinations of aliphatic groups and substituted cyclic groups, combinations of substituted aliphatic groups and substituted cyclic groups, amido groups, substituted amido groups, phosphido groups, substituted phosphido groups, alkoxide groups, substituted alkoxide groups, aryloxide groups, substituted aryloxide groups, organometallic groups, and substituted organometallic groups.
Examples of suitable titanium complexes include, but are not limited to: 
xcex75-cyclopentadienyl(2,6-di-tert-butyl-4-methylphenoxy)titanium(IV) dichloride; 
bis(xcex75-cyclopentadienyldichlorotitanium) oxide; 
xcex75-cyclopentadienyl(3,5-di-tert-butylphenoxy)titanium(IV) dichloride; and 
xcex75-cyclopentadienyl(N,N-bis(trimethylsilyl)amido)titanium(IV) dichloride Preferably, the titanium complex is 
xcex75-cyclopentadienyl titanium(IV) trichloride.
Aluminoxanes are cyclic or linear polymeric aluminum compounds. Cyclic aluminoxanes are represented by the formula R(Rxe2x80x94Alxe2x80x94O)n, and linear aluminoxanes are represented by the formula R(Rxe2x80x94Alxe2x80x94Oxe2x80x94)nAlR. R is an alkyl group having from 1 to about 5 carbon atoms per radical, such as, for example, methyl, ethyl, propyl, butyl, and pentyl, and n is an integer from 1 to about 20. Most preferably, R is methyl, and n is about 4.
The polymerization is conducted in a polymerization zone. The polymerization can be conducted in a solution polymerization process or a slurry polymerization process. A solution polymerization process is preferred. In the solution polymerization process, a hydrocarbon solvent capable of dissolving the dialkenyl-tricyclic-nonaromatic compound, olefin, titanium complex, and the dialkenyl-tricyclic-nonaromatic/olefin polymer is utilized. The solvent can be selected from the group consisting of hexane, cyclohexane, toluene, benzene, xylene, t-butylbenzene, and mixtures thereof. Preferably, the solvent is toluene.
In a solution polymerization process, the temperature is in a range of about 0xc2x0 C. to about 300xc2x0 C. However, it is more preferred when the temperature is in a range of about 20xc2x0 C. to about 200xc2x0 C., and it is most preferred when the temperature is in a range of 50xc2x0 C. to 120xc2x0 C.
In a solution polymerization process, the pressure is in a range of about 100 kPa to about 10000 kPa. However, it is more preferred when the pressure is in the range of about 500 kPa to about 6000 kPa, and it is most preferred when the pressure is in the range of 500 kPa to 5000 kPa.
If a slurry polymerization process is utilized, it is preferred to use a loop slurry reactor. These reactors are well known in the polyethylene polymerization art.
The dialkenyl-tricyclic-nonaromatic/olefin polymer produced by this process comprises about 0.1 to about 90 weight percent polymerized dialkenyl-tricyclic-nonaromatic compound based on the weight of the dialkenyl-tricyclic-nonaromatic/olefin polymer. However, it is more preferred when the dialkenyl-tricyclic-nonaromatic/olefin polymer produced by this process comprises about 20 to about 90 weight percent polymerized dialkenyl-tricyclic-nonaromatic compound based on the weight of the dialkenyl-tricyclic-nonaromatic/olefin polymer, and it is most preferred when the dialkenyl-tricyclic-nonaromatic/olefin polymer produced by this process comprises 40 to 80 weight percent polymerized dialkenyl-tricyclic-nonaromatic based on the weight of the dialkenyl-tricyclic-nonaromatic/olefin polymer.
In a more specific embodiment of this invention, a process is provided to produce an ethylene/DCPD polymer. The process comprises contacting n5-cyclopentadienyl titanium(IV) trichloride, ethylene, dicyclopentadiene, and methylaluminoxane in a solution polymerization process to produce the ethylene/DCPD polymer.
The dialkenyl-tricyclic-nonaromatic/olefin polymer produced is not crosslinked. There is no ring opening as a result of the polymerization reaction. The non-crosslinking of the dialkenyl-tricyclic-nonaromatic/olefin polymer is indicated by its ability to dissolve in a solvent at 70xc2x0 C., such as, for example, trichlorobenzene. Crosslinked polymers typically can be insoluble even at higher temperature. Further evidence of no crosslinking is the nuclear magnetic resonance (NMR) spectrum of the dialkenyl-tricyclic-nonaromatic/olefin polymer shows peaks in the olefinic region of the spectrum which confirms the fact that the non-reacting double bond is still intact. In addition, the spectrum shows that the 5,6-double bond (i.e norbornene ring alkenyl constituent) is the one that is polymerizing.
Divinyl-dicyclo-nonaromatic/olefin polymers can be utilized to produce package film, medical equipment, such as syringes or vials, and optical equipment, such as data storage media, industrial lenses, ophthalmic lenses, projection lenses, automotive lenses, and lamp reflectors.